Heteroaryl substituted hydroxyphenyltriazine uv-absorbers

ABSTRACT

The present invention provides compounds having the formula (1) in which each of the radicals R 1 , R 2 , R 3  and R 4 , independently, represent hydrogen, hydroxy, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, CN or COOR 5 , in which R 5  is C 1 -C 20 -alkyl and Z represents a heterocyclic residue selected from the 2H-benzo[1,2-d]triazol-2-yl, 2H-naphtho[1,2-d]triazol-2-yl, benzimidazol-2-yl, benzoxazol-2-yl and benzofuran-2-yl moieties, optionally substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen or NHCOC 1 -C 4 -alkyl, a process for their preparation, new intermediate benzoxazinones useful for their preparation and use of the compounds of formula (1) as UV-absorbers which have improved absorption spectrum characteristics, superior resistance to exposure to UV light and excellent thermal stability, relative to known triphenyltriazine compounds.

[0001] The present invention relates to new compounds and, inparticular, to new heterocyclic substituted hydroxyphenyltriazinecompounds having excellent absorption spectrum characteristics, goodresistance to exposure to UV light and excellent thermal stability, andto the use of the new compounds as UV absorbers.

[0002] If it is desired to increase the light stability of an organicmaterial, especially a coating, a light stabilizer is usually added. Aclass of light stabilizers which is very frequently employed comprisesthe UV absorbers, which protect the material by absorbing the harmfulradiation via chromophores. An important group of UV absorbers is thetriphenyltriazines, which are described, e.g., in EP-A-434 608, EP-A-520938, U.S. Pat. No. 4,619,956, EP-A-483 488, EP-A-500 496, EP-A-502 816and EP-A-506 615.

[0003] A new group of hydroxyphenyltriazine compounds has now been foundwhich have improved absorption spectrum characteristics, superiorresistance to exposure to UV light and excellent thermal stability,relative to known triphenyltriazine compounds.

[0004] According to the present invention, there are provided compoundshaving the formula:

[0005] in which each of the radicals

[0006] R₁, R₂, R₃ and R₄, independently, represent hydrogen, hydroxy,halogen, C₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, CN or COOR₅, in which R₅ isC₁-C₂₀-alkyl and

[0007] Z represents a heterocyclic residue selected from the2H-benzo[1,2-d]triazol-2-yl, 2H-naphtho[1,2-d]triazol-2-yl,benzimidazol-2-yl, benzoxazol-2-yl and benzofuran-2-yl moieties,optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen orNHCOC₁-C₄-alkyl.

[0008] Preferred compounds according to the invention are those havingthe formula (1) in which R₁ and R₃ each, independently representhydrogen, hydroxy, halogen, C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy, CN or COOR₅, inwhich R₅ is C₁-C₄-alkyl and R₂ and R₄ are hydrogen, compounds in whichR₁ represents hydrogen, hydroxy, chlorine, C₁-C₁₀-alkyl or C₁-C₁₀-alkoxyand R₃ is hydrogen being especially preferable.

[0009] Furthermore, within the scope of the compounds of formula (1),those in which Z is a 2H-benzo[1,2-d]triazol-2-yl or a2H-naphtho[1,2-d]triazol-2-yl residue which is unsubstituted orsubstituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or NHCOC₁-C₄-alkyl andthose in which Z is a benzimidazol-2-yl, benzoxazol-2-yl or abenzofuran-2-yl residue which is unsubstituted or substituted byC₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or NHCOC₁-C₄-alkyl are of particularinterest.

[0010] Particularly preferred compounds are those in which, in formula(1), R₁ represents hydrogen, hydroxy or C₁-C₁₀-alkoxy, R₂, R₃ and R₄ arehydrogen and Z represents a 2H-benzo[1,2-d]triazol-2-yl or a2H-naphtho[1,2-d]triazol-2-yl residue which is unsubstituted orsubstituted by NHCOCH₃.

[0011] When R₁, R₂, R₃ and/or R₄ is halogen, such halogen substituentsare fluorine, bromine, iodine or, especially, chlorine substituents.

[0012] C₁-C₂₀alkyl groups R₁, R₂, R₃ R₄ and/or R₅ may be branched orunbranched such as methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,n-nonyl, n-decyl, n-undecyl, 1-methylundecyl, n-dodecyl,1,1,3,3,5,5-hexamethylhexyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.

[0013] C₁-C₂₀alkoxy groups R₁, R₂, R₃ and/or R₄ may be branched orunbranched such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, isobutoxy, t-butoxy, 2-ethylbutoxy, n-pentoxy, isopentoxy,1-methylpentoxy, 1,3-dimethylbutoxy, n-hexoxy, 1-methylhexoxy,n-heptoxy, isoheptoxy, 1,1,3,3-tetramethylbutoxy, 1-methylheptoxy,3-methylheptoxy, n-octoxy, 2-ethylhexoxy, 1,1,3-trimethylhexoxy,1,1,3,3-tetramethylpentoxy, n-nonoxy, n-decoxy, n-undecoxy,1-methylundecoxy, n-dodecoxy, 1,1,3,3,5,5-hexamethylhexoxy, n-tridecoxy,n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxyand n-eicosoxy groups.

[0014] The new compounds of formula (1) may be prepared by reacting anacid chloride of the formula

[0015] with a salicylamide derivative to yield a benzoxazinonederivative of the formula

[0016] and, subsequently, reacting the compound of formula (3) with abenzamidine hydrochloride of the formula

[0017] whereby R₁, R₂, R₃, R₄ and Z are as previously defined.

[0018] The benzoxazinone compounds of formula (3) are new.

[0019] Consequently, a further aspect of the invention is abenzoxazinone compound of formula (3) in which R₁ and R₂, independently,represent hydrogen, hydroxy, halogen, C₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, CN orCOOR₅, in which R₅ is C₁-C₂₀-alkyl and Z represents a heterocyclicresidue selected from the 2H-benzo[1,2-d]triazol-2-yl,2H-naphtho[1,2-d]triazol-2-yl, benzimidazol-2-yl, benzoxazol-2-yl andbenzofuran-2-yl moieties, optionally substituted by C₁-C₄-alkyl,C₁-C₄-alkoxy, halogen or NHCOC₁-C₄-alkyl.

[0020] Preferred compounds of formula (3) are those in which R₁represents hydrogen, hydroxy or C₁-C₁₀-alkoxy, R₂ is hydrogen and Zrepresents a 2H-benzo[1,2-d]triazol-2-yl or a2H-naphtho[1,2-d]triazol-2-yl residue which is unsubstituted orsubstituted by NHCOCH₃.

[0021] The novel triazine compounds are very good UV absorbers and aretherefore useful as stabilizers for organic polymers, especially coatingmaterials, against damage thereto by light and as light stabilizers fortextile fibre materials.

[0022] Particular advantages of the novel compounds include theirsurprisingly high absorption in the 300 to 400 nm region of theelectromagnetic spectrum. Material stabilized with the compoundsaccording to the invention features outstanding resistance to theeffects of weathering and light, and outstanding photostability of theincorporated stabilizer.

[0023] The materials to be stabilized can be, for example, oils, fats,waxes, cosmetics or biocides. A particularly interesting application isin polymeric materials which are present in plastics, rubbers, paintsand other coating materials, photographic material or adhesives.Examples of polymers and other substrates which can be stabilized inthis way are the following:

[0024] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forexample of cyclopentene or norbomene; furthermore polyethylene (whichoptionally can be crosslinked), for example high density polyethylene(HDPE), polyethylene of high density and high molecular mass (HDPE-HMW),polyethylene of high density and ultra-high molecular mass (HDPE-UHMW),medium density polyethylene (MDPE), low density polyethylene (LDPE),linear low density polyethylene (LLDPE), branched low densitypolyethylene (BLDPE).

[0025] Polyolefins, i.e. polymers of monoolefins exemplified in thepreceding paragraph, in particular polyethylene and polypropylene, canbe prepared by different, and especially by the following, methods:

[0026] a) radical polymerization (normally under high pressure and atelevated temperature); or

[0027] b) catalytic polymerization using a catalyst that normallycontains one or more metals of group IVb, Vb, VIb or VIII of thePeriodic Table. These metals usually have one or more ligands, such asoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, for example onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerizationmedium. The catalysts can be activated by themselves in thepolymerization or further activators may be used, for example metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, the metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified, for example, withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0028] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE);

[0029] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylenelbutadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedunder 1), for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acidcopolymers, LLDPE/ethylene-vinyl acetate copolymers,LLDPE/ethylene-acrylic acid copolymers and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0030] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0031] 5. Polystyrene poly-(p-methylstyrene), poly-(α-methylstyrene).

[0032] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer, and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0033] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene, styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 6), for example thecopolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0034] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubber, chlorinated and brominated copolymer ofisobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinatedpolyethylene, copolymers of ethylene and chlorinated ethylene,epichlorohydrin homo- and copolymers, especially polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride; polyvinylidene fluoride; aswell as copolymers thereof such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.

[0035] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates, polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0036] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinylhalide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

[0037] 11. Polymers derived from unsaturated alcohols and amines of theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in point 1.

[0038] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0039] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain comonomers, for example ethylene oxide;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0040] 14. Polyphenylene oxides and sulfides, and mixtures thereof withstyrene polymers or polyamides.

[0041] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters and polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0042] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene, diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic and/or terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide. Block copolymers of the aforementioned polyamides withpolyolefins, olefin copolymers, ionomers or chemically bonded or graftedelastomers; or with polyethers, e.g. with polyethylene glycol,polypropylene glycol or polytetramethylene glycol. As well as polyamidesor copolyamides modified with EPDM or ABS; and polyamides condensedduring processing (RIM polyamide systems).

[0043] 17. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.

[0044] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalates and polyhydroxybenzoates,as well as block polyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS; andacid-modified polyesters.

[0045] 19. Polycarbonates and polyester carbonates.

[0046] 20. Polysulfones, polyether sulfones and polyether ketones.

[0047] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, urea or melamine on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0048] 22. Drying and non-drying alkyd resins.

[0049] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0050] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example from epoxy acrylates, urethane acrylates orpolyester acrylates.

[0051] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, isocyanates,isocyanurates, polyisocyanates or epoxy resins.

[0052] 26. Crosslinked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for exampleproducts of bisphenol A diglycidyl ethers, bisphenol F diglycidylethers, which are crosslinked by means of customary hardeners, forexample anhydrides or amines, with or without accelerators.

[0053] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andderivatives.

[0054] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABSor PBT/PET/PC.

[0055] The invention therefore also relates to a composition comprising

[0056] (A) an organic material which is sensitive to damage by light,oxygen and/or heat, and

[0057] (B) as stabilizer, a compound of the formula (1).

[0058] The invention also relates to a process for stabilizing organicmaterial against damage by light, oxygen and/or heat, which comprisesadding thereto, as stabilizer, a compound of the formula (1), and to theuse of the compound of the formula (1) for stabilizing organic material.

[0059] The amount of the stabilizer to be used depends on the organicmaterial to be stabilized and on the intended use of the stabilizedmaterial. In general, the novel composition comprises from 0.01 to 15parts by weight, in particular from 0.05 to 10 parts by weight,especially from 0.1 to 5 parts by weight, of the stabilizer (componentB) per 100 parts by weight of component (A).

[0060] The stabilizer (component (B)) can also be a mixture of two ormore compounds of the formula (1). In addition to the novel compounds,the novel compositions can also comprise other stabilizers or otheradditives, for example antioxidants, further light stabilizers, metaldeactivators, phosphites or phosphonites. Examples of these stabilizersare the following:

[0061] 1. Antioxidants

[0062] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(a-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-di-methyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6(1′-methyltridec-1′-yl)phenol and mixtures thereof.

[0063] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioc-tylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

[0064] 1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyloctade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0065] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

[0066] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-hydroxyphenyl)disulfide.

[0067] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0068] 1.7. O—, N— and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydi-benzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0069] 1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0070] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0071] 1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0072] 1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-thydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0073] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0074] 1.13. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hy-droxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0075] 1.14. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpoly-hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0076] 1.15. Esters of β-(3,5-dicyclohexyl4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)ox-amide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0077] 1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hy-droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0078] 1.17. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

[0079] 1.18. Ascorbic acid (vitamin C)

[0080] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclo-hexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino-phenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyidiphenylamines, a mixture of mono- und dialkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin4-ol.

[0081] 2. UV Absorbers and Light Stabilisers

[0082] 2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxy-carbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—]— whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0083] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy4,4′-dimethoxy derivatives.

[0084] 2.3. Esters of substituted and unsubstituted benzoic acids, asfor example 4-tertbutyl-phenyl salicylate, phenyl salicylate,octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxy-benzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0085] 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0086] 2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0087] 2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxy-ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1;2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pen-tamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dode-cy-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4aminopiperidine or1,2,2,6,6-pentamethyl4-aminopiperidine.

[0088] 2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0089] 2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxylphenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,and/or a 2,4bis(4-phenylphenyl)-6-aryl-triazine e.g. of WO 96/28431,such as2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl3-4,6-bis(4-phenylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine.

[0090] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyihydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0091] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol di-phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitriloltriethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-di-yl)phosphite.

[0092] Especially preferred are the following phosphites:

[0093] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168,Ciba-Geigy), tris(nonylphenyl) phosphite,

[0094] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhy-droxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0095] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhy-droxylamine derived from hydrogenated tallow amine.

[0096] 7. Thiosynergists, for example, dilauryl thiodipropionate ordistearyl thiodipropionate.

[0097] 8. Peroxide scavengers, for example esters of β-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

[0098] 9. Polyamide stabilisers, for example, copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

[0099] 10. Basic co-stabilisers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zink pyrocatecholate.

[0100] 11. Nucleating agents, for example, inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds such as ionic copolymers (ionomers).

[0101] 12. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0102] 13. Other additives, for example, plasticisers, lubricants,emulsifiers, pigments, rheology additives, catalysts, flow-controlagents, optical brighteners, flameproofing agents, antistatic agents andblowing agents.

[0103] 14. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643;DE-A-4316611; DE-A-4316622; DE-A4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)4-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-di-methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0104] The type and amount of the further stabilizers added isdetermined by the type of substrate to be stabilized and on its intendeduse; frequently, from 0.1 to 5% by weight, based on the polymer to bestabilized, are used.

[0105] The novel stabilizers can with particular advantage be employedin compositions in which component (A) is a synthetic organic polymer,especially a thermoplastic polymer, a binder for coatings, for examplepaints, or a photographic material. Examples of suitable thermoplasticpolymers are polyolefins and polymers comprising heteroatoms in the mainchain. Preference is also given to compositions in which component (A)is a thermoplastic polymer comprising nitrogen, oxygen and/or sulphur,especially nitrogen or oxygen, in the main chain.

[0106] Also of interest are compositions in which component (A) is apolyolefin, for example polyethylene or polypropylene.

[0107] Incorporation into the organic polymers, for example into thesynthetic organic and, in particular, thermoplastic polymers, can becarried out by addition of the novel triphenyl-substituted triazinecompound and any further additives by the methods conventional in theart. The incorporation can expediently be made before or during shaping,for example by mixing the pulverulent components or by adding thestabilizer to the melt or solution of the polymer, or by applying thedissolved or dispersed compounds to the polymer, with or withoutsubsequent evaporation of the solvent. Elastomers can also be stabilizedas latices. Another way of incorporating the novel mixtures intopolymers comprises adding them before or during polymerization of thecorresponding monomers or before crosslinking.

[0108] The novel compounds can also be added to the plastics to bestabilized in the form of a master batch which comprises thesecompounds, for example, in a concentration of from 2.5 to 25% by weight.

[0109] The novel compounds can expediently be incorporated by thefollowing methods:

[0110] as an emulsion or dispersion (for example to latices or emulsionpolymers)

[0111] as a dry mix during mixing of additional components or polymermixtures

[0112] by direct addition to the processing equipment (for exampleextruders, internal mixers, etc.)

[0113] as a solution or melt.

[0114] The stabilized polymer compositions obtained in this way can beconverted into shaped articles, for example fibres, films, tapes,sheets, sandwich boards, containers, pipes and other profiles, byconventional methods, for example hot pressing, spinning, extrusion orinjection moulding.

[0115] The invention therefore additionally relates to the use of thepolymer composition according to the invention for the production of ashaped article.

[0116] Use in multilayer systems is also of interest. In this case, anovel polymer composition having a relatively high content of novelstabilizer, for example, 5-15% by weight, is applied in a thin film(10-100 μm) to a shaped article made from a polymer containing little orno stabilizer of the formula (1). Application may be made at the sametime as the shaping of the base structure, for example by coextrusion.However, application can also be made to the ready-formed basestructure, for example by lamination with a film or by coating with asolution. The outer layer or layers of the finished article have thefunction of a UV filter, which protects the interior of the article fromUV light. The outer layer preferably contains 5-15% by weight, inparticular 5-10% by weight, of at least one compound of the formula (1).

[0117] The polymers stabilized in this way are notable for highweathering resistance, especially for high resistance to UV light. Thisenables them to retain their mechanical properties and their colour andgloss for a long time even when used outside.

[0118] Likewise of particular interest is the use of the novel compoundof the formula (1) as stabilizers for coatings, for example for paints.The invention therefore also relates to those compositions whosecomponent (A) is a film-forming binder for coatings.

[0119] The novel coating composition preferably comprises 0.01-10 partsby weight of (B), in particular 0.05-10 parts by weight of (B),especially 0.1-5 parts by weight of (B), per 100 parts by weight ofsolid binder (A).

[0120] Multilayer systems are possible here as well, where theconcentration of the novel stabilizer (component (B)) in the outer layercan be relatively high, for example from 1 to 15 parts by weight of (B),in particular 3-10 parts by weight of (B), per 100 parts by weight ofsolid binder (A).

[0121] The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it prevents delamination, i.e. the flaking-offof the coating from the substrate. This advantage is particularlyimportant in the case of metallic substrates, including multilayersystems on metallic substrates.

[0122] The binder (component (A)) can in principle be any binder whichis customary in industry, for example those described in Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim 1991. In general, it is a film-forming binderbased on a thermoplastic or thermosetting resin, predominantly on athermosetting resin. Examples thereof are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

[0123] Component (A) can be a cold-curable or hot-curable binder; theaddition of a curing catalyst may be advantageous. Suitable catalystswhich accelerate curing of the binder are described, for example, inUllmann's Encyclopedia of Industrial Chemistry, Vol. A18, p.469, VCHVeriagsgesellschaft, Weinheim 1991.

[0124] Preference is given to coating compositions in which component(A) is a binder comprising a functional acrylate resin and acrosslinking agent.

[0125] Examples of coating compositions containing specific binders are:

[0126] 1. paints based on cold- or hot-crosslinkable alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins, ifdesired with addition of a curing catalyst;

[0127] 2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

[0128] 3. one-component polyurethane paints based on blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringbaking;

[0129] 4. one-component polyurethane paints based on aliphatic oraromatic urethanes or polyurethanes and hydroxyl group containingacrylate, polyester or polyether resins;

[0130] 5. one-component polyurethane paints based on aliphatic oraromatic urethaneacrylates or polyurethaneacrylates having free aminogroups within the urethane strukture and melamine resins or polyetherresins, if necessary with curing catalyst;

[0131] 6. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

[0132] 7. two-component paints based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester;

[0133] 8. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

[0134] 9. two-component paints based on acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component;

[0135] 10. two-component paints based on acrylate-containing anhydridesand polyepoxides;

[0136] 11. two-component paints based on (poly)oxazolines and acrylateresins containing anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

[0137] 12. two-component paints based on unsaturated polyacrylates andpolymalonates;

[0138] 13. thermoplastic polyacrylate paints based on thermoplasticacrylate resins or eternally crosslinking acrylate resins in combinationwith etherified melamine resins;

[0139] 14. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins.

[0140] In addition to components (A) and (B), the coating compositionaccording to the invention preferably comprises as component (C) a lightstabilizer of the sterically hindered amine type, the2-(2-hydroxyphenyl)-1,3,5-triazine and/or2-hydroxyphenyl-2H-benzotriazole type, for example as mentioned in theabove list in sections 2.1, 2.6 and 2.8. Further examples for lightstabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazine typeadvantageously to be added can be found e.g. in the publications U.S.Pat. No. 4,619,956, EP-A-434608, U.S. Pat. No. 5,198,498, U.S. Pat. Nos.,5322,868, 5,369,140, 5,298,067, WO-94118278, EP-A-704437, GB-A-2297091,WO-96/28431. Of special technical interest is the addition of the2-(2-hydroxyphenyl)-1,3,5-triazines and/or2-hydroxyphenyl-2H-benzotriazoles, especially the2-(2-hydroxyphenyl)-1,3,5-triazines.

[0141] To achieve maximum light stability, it is of particular interestto add sterically hindered amines as set out in the abovementioned listunder 2.6. The invention therefore also relates to a coating compositionwhich in addition to components (A) and (B) comprises as component (C) alight stabilizer of the sterically hindered amine type.

[0142] This stabilizer is preferably a 2,2,6,6-tetraalkylpiperidinederivative containing at least one group of the formula

[0143] in which G is hydrogen or methyl, especially hydrogen.

[0144] Component (C) is preferably used in an amount of 0.05-5 parts byweight per 100 parts by weight of the solid binder.

[0145] Examples of tetraalkylpiperidine derivatives which can be used ascomponent (C) are given in EP-A-356 677, pages 3-17, sections a) to f).These sections of this EP-A are regarded as part of the presentdescription. It is particular expedient to employ the followingtetraalkylpiperidine derivatives:

[0146] bis(2,2,6,6-tetramethylpiperid-4yl) succinate,

[0147] bis(2,2,6,6-tetramethylpiperid-4yl) sebacate,

[0148] bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,

[0149] di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,

[0150] bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,

[0151] tetra(2,2,6,6-tetramethylpiperid-4-yl)butane-1,2,3,tetracarboxylate,

[0152] tetra(1,2,2,6,6-pentamethylpiperidyl)butane-1,2,3,4-tetracarboxylate,

[0153] 2,2,4,4tetramethyl-7-oxa-3,20diaza-21-oxo-dispiro[5.1.11.2]heneicosane,

[0154]8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,

[0155] 1,1-bis-(1,2,2,6,6-pentamethylpiperidine-4-yl-oxycarbonyl)-2-(4-methoxyphenyl)-ethene ,

[0156] or a compound of the formulae

[0157] in which m is 5-50.

[0158] Apart from components (A), (B) and, if used, (C), the coatingcomposition can also comprise further components, examples beingsolvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents,drying catalysts and/or levelling agents. Examples of possiblecomponents are those described in Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim 1991.

[0159] Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example.

[0160] Examples of metal carboxylates are the stearates of Pb, Mn or Zn,the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

[0161] Examples of metal chelates are the aluminium, titanium orzirconium chelates of acetylacetone, ethyl acetylacetate,salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate, and the alkoxides of these metals.

[0162] Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate.

[0163] Examples of amines are, in particular, tertiary amines, forexample tributylamine, triethanolamine, N-methyidiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof. Furtherexamples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride.

[0164] Amino-containing resins are simultaneously binder and curingcatalyst. Examples thereof are amino-containing acrylate copolymers.

[0165] The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

[0166] The novel coating compositions can also be radiation-curablecoating compositions. In this case, the binder essentially comprisesmonomeric or oligomeric compounds containing ethylenically unsaturatedbonds, which after application are cured by actinic radiation, i.e.converted into a crosslinked, high molecular weight form. Where thesystem is UV-curing, it generally contains a photoinitiator as well.Corresponding systems are described in the abovementioned publicationUllmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18,pages 451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

[0167] The coating compositions according to the invention can beapplied to any desired substrates, for example to metal, wood, plasticor ceramic materials. They are preferably used as topcoat in thefinishing of automobiles. If the topcoat comprises two layers, of whichthe lower layer is pigmented and the upper layer is not pigmented, thenovel coating composition can be used for either the upper or the lowerlayer or for both layers, but preferably for the upper layer.

[0168] The novel coating compositions can be applied to the substratesby the customary methods, for example by brushing, spraying, pouring,dipping or electrophoresis; see also Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.

[0169] Depending on the binder system, the coatings can be cured at roomtemperature or by heating. The coatings are preferably cured at 50-150°C., and in the case of powder coatings even at higher temperatures.

[0170] The coatings obtained in accordance with the invention haveexcellent resistance to the damaging effects of light, oxygen and heat;particular mention should be made of the good light stability andweathering resistance of the coatings thus obtained, for example paints.

[0171] The invention therefore also relates to a coating, in particulara paint, which has been stabilized against the damaging effects oflight, oxygen and heat by a content of the compound of the formula (1)according to the invention. The paint is preferably a topcoat forautomobiles. The invention furthermore relates to a process forstabilizing a coating based on organic polymers against damage by light,oxygen and/or heat, which comprises mixing with the coating compositiona mixture comprising a compound of the formula (1); and to the use ofmixtures comprising a compound of the formula (1) in coatingcompositions as stabilizers against damage by light, oxygen and/or heat.

[0172] The coating compositions can comprise an organic solvent orsolvent mixture in which the binder is soluble. The coating compositioncan otherwise be an aqueous solution or dispersion. The vehicle can alsobe a mixture of organic solvent and water. The coating composition maybe a high-solids paint or can be solvent-free (e.g. a powder coatingmaterial). Powder coatings are, for example, those described inUllmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages438-444. The powder coating material may also have the form of apowder-slurry (dispersion of the powder preferably in water).

[0173] The pigments can be inorganic, organic or metallic pigments. Thenovel coating compositions preferably contain no pigments and are usedas a clearcoat.

[0174] Likewise preferred is the use of the coating composition as atopcoat for applications in the automobile industry, especially as apigmented or unpigmented topcoat of the paint finish. Its use forunderlying coats, however, is also possible.

[0175] Preference is also given to the use of the novel compound of theformula (1) in photographic materials as stabilizer against damage bylight, especially by UV light. The invention therefore also relates to aphotographic material comprising a compound of the formula (1).

[0176] The compounds according to the invention can be used forphotosensitive materials of all kinds. For example, they can be employedfor colour paper, colour reversal paper, direct-positive colourmaterial, colour negative film, colour positive film, colour reversalfilm and other materials. They are preferably used, inter alia, forphotosensitive colour material which comprises a reversal substrate orwhich forms positives.

[0177] Furthermore, the novel compounds can be combined with other UVabsorbers, especially those which are dispersible in aqueous gelatin,for example with hydroxyphenylbenzo-triazoles (cf. for example U.S. Pat.Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones,oxanilides, cyanoacrylates, salicylates, acrylonitriles or thiazolines.In this context it is advantageous to employ these further,oil-dissolved UV absorbers in the photographic material in layers otherthan those comprising the novel UV absorbers.

[0178] In particular, it is possible successfully to stabilizephotographic materials similar to those described in U.S. Pat. No.4,518,686.

[0179] The invention therefore additionally relates to a photographicmaterial comprising, on support, a blue-sensitive, a green-sensitiveand/or a red-sensitive silver-halide emulsion layer and, if desired, aprotective layer, with a layer comprising a UV absorber being arrangedabove the uppermost silver-halide emulsion layer, wherein the UVabsorber is a compound of the formula (1).

[0180] Preference is additionally given to photographic materials whichhave a layer comprising a compound of the formula (1) above theuppermost silver-halide emulsion layer and/or between the green- andred-sensitive silver-halide emulsion layers.

[0181] Furthermore, it may be advantageous for all or some of the saidlayers which can comprise a UV absorber to have a UV absorber mixtureand/or a further UV absorber which is dispersible in aqueous gelatin,but a compound of the formula (1) must be present at least in one layer.

[0182] The novel material preferably has gelatin interlayers between thesilver-halide emulsion layers.

[0183] Preference is given to photographic materials in which the silverhalide in the blue-sensitive, green-sensitive and/or red-sensitive layeris silver chloride bromide comprising at least 90 mol % of silverchloride.

[0184] The compounds of the formula (1) which are used in accordancewith the invention can be incorporated, alone or together with thecolour coupler and, if used, further additives, into the colourphotographic material by dissolving the compounds beforehand inhigh-boiling organic solvents. It is preferred to use solvents whichboil at higher than 160° C. Typical examples of such solvents are theesters of phthalic acid, phosphoric acid, citric acid, benzoic acid orof fatty acids, and also alkylamides and phenols.

[0185] Preferred colour couplers for use in the compositions of theinvention, examples of such compounds, further additives such as colourcast inhibitors, DIR couplers and further light stabilizers, such as UVabsorbers, phenols, phosphorus(III) compounds, organometallic complexes,hydroquinones and hydroquinone ethers, and more precise details on thestructure of various photographic materials, can be found, for example,in the publications EP-A-531 258 and EP-A-520 938, and in the literaturecited therein.

[0186] The novel triazine compounds of the formula (1) are also suitablefor use in a process for the photochemical stabilization of undyed, dyedor printed fibre materials comprising for example, silk, leather, wool,polyamide, polyester or polyurethanes, and especiallycellulose-containing fibre materials of all kinds. This process forms afurther aspect of the present invention. Examples of such fibrematerials are the natural cellulose fibres, such as cotton, linen, juteand hemp, and also viscose staple fibre and regenerated cellulose.Preferred textile fibre materials are those of cotton or polyester. Thenovel triphenyl-substituted triazine compounds are also suitable for thephotochemical stabilization of hydroxyl-containing fibres in blendfabrics, for example blends of cotton with polyester fibres or polyamidefibres. A further preferred area of application relates to the blockingor reduction of the UV radiation which passes through the abovementionedtextile materials (UV cutting) and the heightened sun protection whichtextile materials finished with a novel compound offer to the humanskin.

[0187] As textile fibre material to be treated, polyester- or celluloseacetate-containing fibre materials are of particular interest. Examplesof polyester fibres are, e.g., cellulose ester fibres such ascellulose-21/2-acetate fibres and -triacetate fibres, especially linearpolyester fibres, optionally those modified with acid. These polyesterfibres may be obtained by condensation of terephthalic acid with1,4-bis(hydroxymethyl)-cyclohexane. Also of interest are fibres fromcopolymers of terephthalic- and isophthalic acid and ethylene glycol.Conventional polyester fibres in the textile industry are particularlythose comprising terephthalic acid and ethylene glycol.

[0188] The textile material to be treated may also be a mixed fabric ofpolyester fibres and other fibres, e.g., polyacrylonitrile/polyester-,polyamide/polyester-, polyester/cotton-, polyestermscose- orpolyester/wool mixed fibres, which may be discontinuously orcontinuously dyed or printed in conventional manner.

[0189] The textile material can be used in various forms, for example aspiece goods such as knitted goods or fabrics, or as yarns, e.g. oncheeses or warp beams.

[0190] Also very suitable for use in the process of the presentinvention are textile fabrics which are used in the outerwear garmentsector and which are at least partly permeable to light. By the use ofsuch textiles, treated according to the process of the presentinvention, skin tissue under the outerwear garment can be protectedagainst the damaging effects of UV-radiation. This protective effect isknown as UV-cutting and is manifested in that the textile fibre materialtreated with a compound of formula (1) has a significantly increasedUltraviolet Protection Factor (UPF), relative untreated textile fibematerial.

[0191] The UPF is defined as the quotient of the dose of UV radiationwhich damages protected skin to that which damages unprotected skin.Accordingly, a UPF is also a measure of the extent to which untreatedfibre materials and fibre materials treated with a novel compound of theformula (1) are permeable to UV radiation. The determination of theultraviolet protection factor of textile fibre materials is explained,for example, in WO 94/04515 or in J. Soc. Cosmet. Chem. 40, 127-133(1989) and can be carried out analogously thereto.

[0192] The compound of formula (1) is added in an amount of 0.01 to 5%by weight, preferably 0.1 to 3% by weight and, in particular, from 0.25to 2% by weight, based on the weight of the fibre material.

[0193] The compound of formula (1) is only sparingly soluble in waterand are therefore applied in dispersed form. The dispersions are formedby grinding the compound of formula (1) in water, using an appropriatedispersing agent, with the aid, e.g., of quartz spheres and a high-speedstirrer, until the particle size required for applicational conditionshas been attained.

[0194] Examples of dispersing agents for the compounds of formula (1)include, e.g.:

[0195] acid esters or their salts of alkylene oxide adducts, such asacid esters or their salts of a polyadduct of 4 to 40 mol ethylene oxideon 1 mol of a phenol, or phosphoric acid esters of the adducts of 6 to30 mol ethylene oxide on 1 mol of 4-nonylphenol, on 1 mol ofdinonylphenol or, especially, on 1 mol of compounds which are producedby addition of 1 to 3 mol of optionally substituted styrenes on to 1 molof phenol;

[0196] polystyrene sulfonates;

[0197] fatty acid taurides;

[0198] alkylated diphenyl oxide-mono- or -di-sulfonates;

[0199] sulfonates of polycarboxylic acid esters;

[0200] addition products, converted into an acid ester with an organicdicarboxylic acid or an inorganic polybasic acid, of 1 to 60, preferably2 to 30 mol of ethylene oxide and/or propylene oxide, on C₈-C₂₂-fattyamines, fatty amides, fatty acids or fatty alcohols, or onC₃-C₆-alcohols having 3-6 hydroxy groups;

[0201] lignin sulfonates; and, particularly preferably

[0202] formaldehyde-condensation products such as condensation productsof lignin sulfonates and/or phenol and formaldehyde, condensationproducts of formaldehyde with aromatic sulfonic acids, such ascondensation products of ditolylether sulfonates and formaldehyde,condensation products of naphthalene sulfonic acids and/or naphthol- ornaphthylamine-sulfonic acids with formaldehyde, condensation products ofphenol sulfonic acids and/or sulfonated dihydroxydiphenylsulfone andphenols or cresols with formaldehyde and/or urea, as well ascondensation products of diphenyloxide-disulfonic acid derivatives withformaldehyde.

[0203] The textile material to be stabilised is preferably dyed textilematerial, in particular textile material dyed with dispersion dyes whichare only slightly soluble in water. These dyes are therefore present inthe dye liquor predominately as a fine dispersion. They may be ofvarious dyes classes such as the acridone-, azo-, anthraquinone-,coumarine-, methine-, perinone-, naphthoquinoneimine-, quinophthalone-,styryl- or nitro-dye classes. Mixtures of dispersion dyes can also beused according to the present invention.

[0204] The dyeings are conducted from aqueous baths using a continuousor discontinuous process. For discontinuous processes (exhaustionprocesses), the liquor ratio can be selected from within a wide range,e.g. 1:1 to 1:100, preferably 1:6 to 1:50. The dyeing temperature is atleast 50° C. and is generally not higher than 140° C. Preferably thedyeing temperature is in the range of from 80 to 135° C.

[0205] For continuous processes, the dye baths, which can containfurther auxiliaries as well as the dyes, are applied to the piece goods,for example by foularding, spraying or slop padding, and are developedby thermofixing or high temperature steam processes.

[0206] Linear polyester fibres and cellulose fibres are preferably dyedby the so-called high temperature processes, in closed andpressure-resistant apparatus, at temperatures above 100° C., preferablybetween 110 and 135° C. and optionally under pressure. Suitable closedvessels are, e.g., circulation apparatus, such as cheese- or beam dyeingmachines, winch vats, jet- or drum dyeing machines, muff-dyeingapparatus, paddles or jiggers.

[0207] Cellulose-21/2-acetate fibres are preferably dyed at temperaturesof 80-85° C.

[0208] If the compounds of formula (1) are added during the dyeingapplication, they may be so applied that the fibre material is firsttreated with them and the dyeing is then conducted or, preferably, thefibre material is treated simultaneously with the compounds of formula(1) and the dyestuff in the dyebath. The application of the compounds offormula (1) can also be effected, however, subsequently on the finisheddyeing by means of thermofixing, e.g. at 190 to 230° C. over a period of30 seconds to 5 minutes. A pretreatment with the compounds of formula(1) is also possible, whereby the textile material is simultaneouslysurface-fixed.

[0209] The dye liquors can also contain further additives such as dyeingauxiliaries, dispersing agents, carriers, wool protection- and wettingagents, as well as de-foamers.

[0210] Moreover, the dye baths can contain mineral acids such assulfuric acid or phosphoric acid, or expediently organic acids such asaliphatic carboxylic adds, e.g. formic acid, acetic acid, oxalic acid orcitric acid and/or salts such as ammonium acetate, ammonium sulfate orsodium acetate. The acids are used particularly for the adjustment ofthe pH-value of the dye bath used, the pH-value lying preferably between4 and 5.

[0211] Preferably, the fibre material is placed initially for 5 minutesat 40 to 80° C. in the bath which contains the dye, the stabilisercompounds of formula (1) and optionally further additives, and which isadjusted to a pH-value of 4.5 to 5.5, the temperature is increased to125 to 130° C. over 10 to 20 minutes, and is further treated at thistemperature for 15 to 90 minutes, preferably for 30 minutes.

[0212] The finishing of the dyeings is effected by cooling the dyeliquor to 50 to 80° C., by rinsing the dyeings with water and optionallyby cleaning in conventional manner in alkaline medium under reductiveconditions. The dyeings are then rinsed again and dried. If vat dyes areused for the cellulose component, the goods are first treated withhydrosulfite at a pH-value of 6 to 12.5, in conventional manner, thentreated with an oxidising agent and finally washed out.

[0213] For the production of prints, the stabiliser compounds of formula(1), in the form of their aqueous dispersions, are mixed with theprinting pastes. The printing pastes contain e.g. 0.1 to 10%, preferably0.1 to 5%, of the corresponding stabiliser compounds of formula (1),based on the weight of the printing paste.

[0214] The amount of the dyestuff which is added to the printing pastedepends on the desired colour shade; generally, amounts of 0.01 to 15,preferably 0.02 to 10 weight %, based on the textile material used,suffice.

[0215] In addition to the dyestuffs and the aqueous dispersions of thestabiliser compounds of formula (1), the printing pastes alsoconveniently contain acid-stable thickeners, preferably those of naturalorigin such as carob bean flour derivatives, especially sodium alginate,either used alone or mixed with modified cellulose, especially withpreferably 20 to 25 weight % of carboxymethylcellulose. The printingpastes can also contain acid donors such as butyrolactone or sodiumhydrogen phosphate, stabilisers, sequestering agents, emulsifiers,water-insoluble solvents, oxidising agents or deaerating agents.

[0216] Preferred stabilisers are formaldehye-liberating agents, such asparaformaldehyde or trioxan, especially aqueous solutions containing 3040-weight % of formaldehyde; sequestering agents are e.g. sodiumnitrilotriacetate, sodium ethylenediaminotetraacetate, especially sodiumpolymetaphosphate, in particular sodium hexametaphosphate; emulsifiersare preferably adducts of an alkylene oxide and a fatty alcohol,especially an adduct of oleyl alcohol and ethylene oxide;water-insoluble solvents are preferably high-boiling, saturatedhydrocabons, especially paraffins having a boiling range of 160 to 210°C. (so-called white spirits); oxidising agents are e.g. aromaticnitro-compounds, preferably aromatic mono- or di-nitrocarboxylic acidsor -suffonic acids, which are optionally used as alkylene oxide adducts,especially nitrobenzene suffonic acids; and deaerating agents are e.g.high-boiling solvents, preferably turpentine oils, higher alcohols,preferably C₈-C₁₀-alcohols, terpene alcohols or deaerating agents basedon mineral- and/or silicone oils, especially commercial formulations ofabout 15 to 25 weight % of a mineral- and silicone oil mixture and about75 to 85 weight % of a C₈-C₁₀-alcohol, such as 2-ethyl-n-hexanol.

[0217] For the printing of the fibre material, the printing paste may beapplied directly to the whole or part of the surface, conveniently usingprinting machines of conventional construction, typically ink-jetprinting-, Vigoureux printing-, rotogravure printing-, rotary screenprinting and surface screen printing machines.

[0218] After the printing, the fibre material may be dried attemperatures up to 150° C., preferably at 80 to 120° C.

[0219] The subsequent fixation of the fibre material is usually effectedby a heat treatment at temperatures of preferably 100 to 220° C. Theheat treatment is generally conducted using superheated steam underpressure. Depending on the temperature, the fixation may need from 20seconds to 10 minutes, preferably 4 to 8 minutes.

[0220] The prints are finished in conventional manner by rinsing withwater, followed by an optional additional cleaning in alkaline mediumunder reductive conditions, e.g. using sodium dithionite. In the lattercase, the print dyeings are again rinsed, de-watered and dried.

[0221] The textile fibres treated with the stabiliser compounds offormula (1) have good resistance to the damaging effects of light,oxygen and heat. In particular, the stabilisation process according tothe present invention enables to provision of polyester dyeings andprints which exhibit high lightfastness and high resistance tosublimation. No specific pre- or after-treatment of the fibre materialis necessary with the stabilisation process according to the presentinvention.

[0222] The UV absorbers according to the invention are suitable,furthermore, as photoprotective agents in cosmetic preparations.

[0223] The invention additionally relates, therefore, to a cosmeticpreparation comprising at least one compound of the formula (1) andcosmetically acceptable carriers or auxiliaries.

[0224] The novel cosmetic composition contains from 0.1 to 15% byweight, preferably from 0.5 to 10% by weight, based on the overallweight of the composition, of a UV absorber of the formula (1) and acosmetically acceptable auxiliary.

[0225] The cosmetic composition can be prepared by physically mixing thenovel UV absorber with the auxiliary by means of customary methods, forexample by simply stirring together the two materials. Preferably,however, the sparingly water-soluble or water-insoluble UV absorber ofthe formula (1) is ground to a mean particle size of 100-400 nm or less,for example by wet-grinding in water using a suitable grinding aid andwith the addition of conventional auxiliary such as a surfactant or apolymer or a mixture thereof. the nanopigment so obtained isincorporated into a conventional sun protection formulation. Theproduction of oil-in-water or water-in-oil emulsions containing one ormore pigments and in the presence of one or more oil- or water-solubleUV absorber of the formula (1) may be conducted using known methods forthe preparation of sun protection emulsions.

[0226] The cosmetic preparation according to the invention can beformulated as a water-in-oil or oil-in-water emulsion, as an oil-in-oilalcohol lotion, as a vesicular dispersion of an ionic or nonionicamphiphilic lipid, as a gel, solid stick or as an aerosol formulation.

[0227] As a water-in-oil or oil-in-water emulsion, the cosmeticallyacceptable auxiliary preferably contains from 5 to 50% of an oily phase,from 5 to 20% of an emulsifier and from 30 to 90% water. The oil phasementioned can comprise any oil which is suitable for cosmeticformulations, for example one or more hydrocarbon oils, a wax, a naturaloil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferredmono or polyols are ethanol, isopropanol, propylene glycol, hexyleneglycol, glycerol and sorbitol.

[0228] For the cosmetic formulations according to the invention it ispossible to use any conventionally employed emulsifier, for example oneor more ethoxylated esters of naturally occurring derivatives, forexample polyethoxylated esters of hydrogenated castor oil; or a siliconeoil emulsifier such as silicone polyol; an unmodified or ethoxylatedfatty acid soap; an ethoxylated fatty alcohol; an unmodified orethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylatedglyceride.

[0229] The cosmetic formulation can also comprise further components,for example emollients, emulsion stabilizers, skin moisteners, tanningaccelerators, thickeners such as xanthan, moisture retention agents suchas glycerol, preservatives, or fragrances and colourants.

[0230] The novel cosmetic formulations are notable for good protectionof human skin and/or hair against the damaging effect of sunlight whileat the same time providing for reliable tanning of the skin.

[0231] The following Examples further illustrate the present invention.

EXAMPLE 1

[0232] a) 50 g of 4-(2H-naphtho[1,2-d]triazol-2-yl) benzoic acid,prepared according to Chem. Ber., 119, 1627-1639 (1986), are slurried in1000 ml of toluene, the slurry warmed to 70° C. and 41.2 g of thionylchloride added. After stirring for 10 hours at 100° C., gas evolutionceases. The reaction mixture is filtered and the toluene solutionevaporated to dryness. There are obtained 39.4 g of a beige solidcompound of formula

[0233] characterized by the following elemental analysis:

[0234] C₁₇H₁₀CIN₃O requires: C 66.35%; H 3.28%; N 13.65%; Cl 11.52% andO 5.20%;

[0235] found: C 66.58%; H 3.36%; N 13.22%; Cl 11.38% and O 5.59%.

[0236] b) 30.8 g of the acid chloride (101a), 15.07 g of salicylamideand 1 ml of piperidine are added to 160 ml of xylene, the mixture heatedto 140-145° C. and stirred at this temperature for 6 hours, during whichtime 1.3 ml of water are removed by way of a Dean and Stark apparatus.The solution is then evaporated to dryness to yield 51.5 g of a beigecompound of formula

[0237] c) 21.0 g of the compound of formula (101b) are suspended in 200ml of methyl cellusolve, the suspension warmed to 80° C. and treated,over 5 minutes, with 22.9 g of a 38% solution of benzamidinehydrochloride in methanol. 32.7 g of a 30% sodium methylate solution inmethanol are then added dropwise over 5 minutes, when a light beigeprecipitate results. The mixture is stirred for a further 4 hours at 90°C., cooled to 60° C. and filtered. There are obtained 12.6 g of ayellowish compound of formula

[0238] characterized by the following elemental analysis:

[0239] C₃₁H₂₀N₆O requires: C 75.60%; H 4.09%; N 17.06%; and O 3.25%;

[0240] found: C 75.11%; H 4.05%; N 16.88%; and O 3.94%

[0241] and by a λ_(max) at 360 nm with an extinction coefficient ε of54230.

[0242] By proceeding in a manner analogous to that described in Example1, but employing the appropriate starting materials, the compounds ofgeneral formulae (5) and (6) depicted in the following Tables 1 and 2are obtained: TABLE 1 (5)

Example Nr. R′ λ_(max) (nm) ε 102 OH 357 56700 103 OCH₂CH(C₂H₅)C₄H₉ 35760836

[0243] TABLE 2 (6)

Example Nr R″ R″′ λ_(max) (nm) ε 104 H H 337 54734 105 H OH 338 56324106 NHCOCH₃ H 364 39665

1. A compound having the formula

in which each of the radicals R₁, R₂, R₃ and R₄, independently,represent hydrogen, hydroxy, halogen, C₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, CN orCOOR₅, in which R₅ is C₁-C₂₀-alkyl and Z represents a heterocyclicresidue selected from the 2H-benzo[1,2-d]triazol-2-yl,2H-naphtho[1,2-d]triazol-2-yl, benzimidazol-2-yl, benzoxazol-2-yl andbenzofuran-2-yl moieties, optionally substituted by C₁-C₄-alkyl,C₁-C₄-alkoxy, halogen or NHCOC₁-C₄-alkyl.
 2. A compound according toclaim 1 in which R₁ and R₃ each, independently represent hydrogen,hydroxy, halogen, C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy, CN or COOR₅, in which Rsis C₁-C₄-alkyl and R₂ and R₄ are hydrogen.
 3. A compound according toclaim 2 in which R₁ represents hydrogen, hydroxy, chlorine, C₁-C₁₀-alkylor C₁-₁₀-alkoxy and R₃ is hydrogen.
 4. A compound according to any oneof claims 1 to 3 in which Z is a 2H-benzo[1,2-d]triazol-2-yl or a2H-naphtho[1,2-d]triazol-2-yl residue which is unsubstituted orsubstituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or NHCOC₁-C₄-alkyl. 5.A compound according to any one of claims 1 to 3 in which Z is abenzimidazol-2-yl, benzoxazol-2-yl or a benzofuran-2-yl residue which isunsubstituted or substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen orNHCOC₁-C₄-alkyl.
 6. A process for the preparation of a compound offormula (1), characterized by reacting an acid chloride of the formula

with a salicylamide derivative to yield a benzoxazinone derivative ofthe formula

and, subsequently, reacting the compound of formula (3) with abenzamidine hydrochloride of the formula

whereby R₁, R₂, R₃, R₄ and Z are as defined in claim
 1. 7. A compound ofthe formula

in which R₁, R₂ and Z are as defined in claim
 1. 8. A compositioncomprising (A) an organic material which is sensitive to damage bylight, oxygen and/or heat, and (B) as stabilizer, a compound accordingto any one of claims 1 to
 5. 9. A composition according to claim 8comprising from 0.01 to 15 parts by weight of component (B), per 100parts by weight of component (A).
 10. A composition according to claim 8or 9 comprising, In addition to components (A) and (B), one or morefurther stabilizers or further additives.
 11. A composition according toany of claims 8 to 10 comprising, as component (A), a synthetic organicpolymer.
 12. A composition according to any of claims 8 to 11comprising, as component (A), a thermoplastic polymer, a binder forcoatings or a photographic material.
 13. A composition according toclaim 10 comprising, as component (A), a binder for coatings and, asadditional component C), one or more stabilizers selected from lightstabilizers of the sterically hindered amine and/or2-hydroxyphenyl-2H-benzotriazole type.
 14. A composition according toclaim 13 in which component C) is present in an amount of 0.05 to 5parts by weight, per 100 parts by weight of the binder.
 15. Acomposition according to claim 8 in which the organic material which issensitive to damage by light, oxygen and/or heat is an undyed, dyed orprinted fibre material.
 16. A method of increasing the sun protectionfactor of textile fibre materials, which comprises applying to the fibrematerials a compound according to any one of claims 1 to 5, in anaqueous or aqueous-organic solution, and then fixing this compound. 17.A cosmetic preparation comprising at least one compound according to anyone of claims 1 to 5 and a cosmetically acceptable auxiliary.
 18. Aprocess for stabilizing organic material against damage by light, oxygenand/or heat, which comprises adding to this material a stabilizercomprising one or more compounds according to any one of claims 1 to 5.19. Use of a compound according to any one of claims 1 to 5 as asunscreen for the human skin.